Acta Cryst. (2008). E64, m176 [ doi:10.1107/S1600536807065555 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-1-cyclopropyl-6-fluoro-4-oxido-7-(1-piperazinyl)-1,4-dihydroquinoline-3-carboxylato]nickel(II)]In the title compound, [Ni(C17H17FN3O3)2]n, the NiII atom exists in a distorted trans-NiN2O4 octahedral geometry defined by two monodentate N-bonded and two bidentate O,O-bonded 1-cyclopropyl-6-fluoro-4-oxido-7-(1-piperazinyl)-1,4-dihydroquinoline-3-carboxylate (ciprofloxacinium) monoanions. The extended two-dimensional structure is a square grid. The Ni atom lies on a center of inversion.
A mixture of Ni(NO3)2.6H2O (0.07 g, 0.25 mmol), ciprofloxacin hydrochloride (0.19 g, 0.5 mmol), and water (12 ml) was stirred for 30 min in air. The mixture was then transferred to a 23 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 72 h under autogenous pressure. Green single crystals of the title compound suitable for X-ray analysis were obtained from the reaction mixture after cooling. Green blocks of (I) with a yield of 21%. Anal. Calc. for C34H34F2N6O6Ni: C 56.77, H 4.73, N 11.69%, O 13.36; Found: C 56.73, H 4.78, N 11.64%, O 13.40.
The carbon-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atom was located in a difference map and refined with a distance restraint of 0.86 (1) Å and the constraint Uiso(H) = 1.2Ueq(N).
Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).
![[Figure 1]](./cs2060fig1thm.gif)
| Fig. 1. The asymmetric unit of the title compound, extended to show the Ni coordination, showing 50% displacement ellipsoids and the atom-numbering scheme [symmetry codes: (i)x, y, z; (ii)-x, y + 1/2, -z + 1/2; (iii)-x, -y, -z; (iv)x, -y - 1/2, z - 1/2] |
![[Figure 2]](./cs2060fig2thm.gif)
| Fig. 2. A view of part of a two-dimensional polymeric sheet in the crystal of the title compound showing the square-grid connectivity. |
| [Ni(C17H17FN3O3)2] | F000 = 748 |
| Mr = 719.38 | Dx = 1.435 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| a = 5.9999 (6) Å | Cell parameters from 2967 reflections |
| b = 21.437 (2) Å | θ = 2.5–27.3º |
| c = 13.2287 (14) Å | µ = 0.65 mm−1 |
| β = 101.886 (2)º | T = 295 (2) K |
| V = 1665.0 (3) Å3 | Block, green |
| Z = 2 | 0.34 × 0.26 × 0.18 mm |
| Bruker SMART CCD diffractometer | 2890 independent reflections |
| Radiation source: fine-focus sealed tube | 2466 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.030 |
| T = 295(2) K | θmax = 25.1º |
| ω scans | θmin = 2.5º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→7 |
| Tmin = 0.810, Tmax = 0.892 | k = −25→21 |
| 8098 measured reflections | l = −15→15 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.173 | w = 1/[σ2(Fo2) + (0.1083P)2 + 3.3784P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.008 |
| 2890 reflections | Δρmax = 1.92 e Å−3 |
| 226 parameters | Δρmin = −0.43 e Å−3 |
| 1 restraint | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Ni(C17H17FN3O3)2] | V = 1665.0 (3) Å3 |
| Mr = 719.38 | Z = 2 |
| Monoclinic, P21/c | Mo Kα |
| a = 5.9999 (6) Å | µ = 0.65 mm−1 |
| b = 21.437 (2) Å | T = 295 (2) K |
| c = 13.2287 (14) Å | 0.34 × 0.26 × 0.18 mm |
| β = 101.886 (2)º |
| Bruker SMART CCD diffractometer | 2890 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2466 reflections with I > 2σ(I) |
| Tmin = 0.810, Tmax = 0.892 | Rint = 0.030 |
| 8098 measured reflections |
| R[F2 > 2σ(F2)] = 0.057 | 1 restraint |
| wR(F2) = 0.173 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | Δρmax = 1.92 e Å−3 |
| 2890 reflections | Δρmin = −0.43 e Å−3 |
| 226 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Ni1 | 0.0000 | 0.5000 | 0.5000 | 0.0191 (2) | |
| F1 | 0.7020 (4) | 0.74254 (11) | 0.67877 (19) | 0.0407 (6) | |
| O1 | −0.2122 (4) | 0.48858 (11) | 0.6010 (2) | 0.0254 (6) | |
| O2 | −0.3432 (6) | 0.49499 (14) | 0.7453 (3) | 0.0489 (9) | |
| O3 | 0.1687 (4) | 0.56702 (11) | 0.59535 (18) | 0.0246 (5) | |
| N1 | 0.0052 (5) | 0.65173 (14) | 0.8485 (2) | 0.0275 (7) | |
| N2 | 0.5762 (5) | 0.81201 (14) | 0.8367 (2) | 0.0266 (7) | |
| N3 | 0.7552 (5) | 0.93356 (13) | 0.9140 (2) | 0.0244 (6) | |
| C1 | −0.2146 (6) | 0.51226 (17) | 0.6881 (3) | 0.0261 (8) | |
| C2 | −0.0603 (6) | 0.56768 (15) | 0.7245 (3) | 0.0236 (7) | |
| C3 | −0.1042 (6) | 0.59953 (17) | 0.8074 (3) | 0.0274 (8) | |
| H3 | −0.2188 | 0.5841 | 0.8383 | 0.033* | |
| C4 | 0.1761 (6) | 0.67679 (16) | 0.8044 (3) | 0.0242 (7) | |
| C5 | 0.2833 (6) | 0.73317 (17) | 0.8400 (3) | 0.0264 (8) | |
| H5 | 0.2370 | 0.7542 | 0.8937 | 0.032* | |
| C6 | 0.4567 (6) | 0.75847 (16) | 0.7975 (3) | 0.0243 (7) | |
| C7 | 0.5192 (6) | 0.72338 (17) | 0.7174 (3) | 0.0253 (8) | |
| C8 | 0.4147 (6) | 0.67009 (16) | 0.6793 (3) | 0.0251 (7) | |
| H8 | 0.4605 | 0.6498 | 0.6249 | 0.030* | |
| C9 | 0.2363 (6) | 0.64486 (16) | 0.7215 (3) | 0.0232 (7) | |
| C10 | 0.1164 (6) | 0.58960 (15) | 0.6756 (3) | 0.0216 (7) | |
| C11 | −0.0674 (7) | 0.6856 (2) | 0.9317 (3) | 0.0345 (9) | |
| H11 | −0.1386 | 0.7262 | 0.9124 | 0.041* | |
| C12 | 0.0698 (10) | 0.6814 (3) | 1.0393 (4) | 0.0550 (13) | |
| H12A | 0.0834 | 0.7187 | 1.0817 | 0.066* | |
| H12B | 0.2035 | 0.6548 | 1.0512 | 0.066* | |
| C13 | −0.1585 (10) | 0.6507 (3) | 1.0120 (4) | 0.0632 (16) | |
| H13A | −0.1629 | 0.6055 | 1.0075 | 0.076* | |
| H13B | −0.2829 | 0.6694 | 1.0379 | 0.076* | |
| C14 | 0.6114 (8) | 0.86219 (18) | 0.7651 (3) | 0.0360 (9) | |
| H14A | 0.4703 | 0.8850 | 0.7425 | 0.043* | |
| H14B | 0.6543 | 0.8441 | 0.7047 | 0.043* | |
| C15 | 0.7969 (7) | 0.90671 (18) | 0.8177 (3) | 0.0347 (9) | |
| H15A | 0.9409 | 0.8846 | 0.8324 | 0.042* | |
| H15B | 0.8105 | 0.9403 | 0.7703 | 0.042* | |
| C16 | 0.7067 (9) | 0.8829 (2) | 0.9801 (3) | 0.0464 (12) | |
| H16A | 0.6634 | 0.9008 | 1.0406 | 0.056* | |
| H16B | 0.8452 | 0.8591 | 1.0035 | 0.056* | |
| C17 | 0.5196 (8) | 0.8385 (2) | 0.9285 (3) | 0.0458 (12) | |
| H17A | 0.5018 | 0.8054 | 0.9762 | 0.055* | |
| H17B | 0.3764 | 0.8609 | 0.9104 | 0.055* | |
| H3N | 0.641 (6) | 0.9588 (19) | 0.902 (4) | 0.055* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0266 (4) | 0.0117 (4) | 0.0186 (4) | 0.0001 (2) | 0.0035 (3) | −0.0027 (2) |
| F1 | 0.0451 (13) | 0.0358 (13) | 0.0491 (14) | −0.0169 (10) | 0.0284 (11) | −0.0146 (11) |
| O1 | 0.0311 (13) | 0.0194 (12) | 0.0252 (13) | −0.0048 (10) | 0.0042 (10) | −0.0037 (10) |
| O2 | 0.067 (2) | 0.0467 (19) | 0.0417 (18) | −0.0339 (15) | 0.0306 (17) | −0.0182 (13) |
| O3 | 0.0307 (13) | 0.0206 (12) | 0.0240 (12) | −0.0021 (10) | 0.0090 (10) | −0.0075 (10) |
| N1 | 0.0331 (16) | 0.0258 (16) | 0.0263 (16) | −0.0096 (12) | 0.0123 (13) | −0.0114 (12) |
| N2 | 0.0389 (17) | 0.0178 (14) | 0.0245 (15) | −0.0098 (12) | 0.0101 (13) | −0.0055 (12) |
| N3 | 0.0304 (16) | 0.0155 (14) | 0.0268 (15) | −0.0031 (11) | 0.0044 (12) | −0.0007 (12) |
| C1 | 0.0301 (19) | 0.0209 (17) | 0.0271 (19) | −0.0049 (14) | 0.0055 (15) | −0.0005 (14) |
| C2 | 0.0299 (18) | 0.0164 (17) | 0.0236 (17) | −0.0038 (13) | 0.0040 (14) | −0.0030 (13) |
| C3 | 0.0317 (18) | 0.0248 (18) | 0.0267 (18) | −0.0058 (14) | 0.0081 (15) | −0.0016 (15) |
| C4 | 0.0285 (18) | 0.0204 (17) | 0.0246 (18) | −0.0042 (14) | 0.0077 (14) | −0.0044 (14) |
| C5 | 0.0320 (19) | 0.0224 (17) | 0.0260 (18) | −0.0060 (15) | 0.0088 (15) | −0.0087 (14) |
| C6 | 0.0286 (18) | 0.0185 (17) | 0.0251 (18) | −0.0042 (14) | 0.0044 (14) | −0.0041 (14) |
| C7 | 0.0291 (18) | 0.0239 (18) | 0.0253 (18) | −0.0054 (14) | 0.0108 (14) | −0.0036 (14) |
| C8 | 0.0312 (18) | 0.0216 (17) | 0.0241 (17) | −0.0019 (14) | 0.0092 (14) | −0.0039 (14) |
| C9 | 0.0257 (17) | 0.0217 (17) | 0.0227 (17) | −0.0029 (13) | 0.0058 (13) | −0.0039 (13) |
| C10 | 0.0261 (17) | 0.0156 (16) | 0.0221 (17) | 0.0016 (13) | 0.0024 (13) | −0.0002 (13) |
| C11 | 0.040 (2) | 0.033 (2) | 0.034 (2) | −0.0064 (17) | 0.0166 (17) | −0.0116 (17) |
| C12 | 0.078 (3) | 0.056 (3) | 0.030 (2) | −0.009 (3) | 0.009 (2) | −0.014 (2) |
| C13 | 0.094 (4) | 0.063 (3) | 0.046 (3) | −0.029 (3) | 0.045 (3) | −0.017 (2) |
| C14 | 0.058 (3) | 0.0240 (19) | 0.0253 (19) | −0.0120 (17) | 0.0057 (18) | −0.0016 (15) |
| C15 | 0.050 (2) | 0.029 (2) | 0.029 (2) | −0.0149 (17) | 0.0159 (17) | −0.0059 (16) |
| C16 | 0.074 (3) | 0.039 (2) | 0.029 (2) | −0.035 (2) | 0.018 (2) | −0.0119 (18) |
| C17 | 0.064 (3) | 0.041 (2) | 0.040 (2) | −0.032 (2) | 0.028 (2) | −0.0232 (19) |
| Ni1—O3 | 2.038 (2) | C5—C6 | 1.391 (5) |
| Ni1—O3i | 2.038 (2) | C5—H5 | 0.9300 |
| Ni1—O1i | 2.041 (3) | C6—C7 | 1.411 (5) |
| Ni1—O1 | 2.041 (3) | C7—C8 | 1.350 (5) |
| Ni1—N3ii | 2.189 (3) | C8—C9 | 1.412 (5) |
| Ni1—N3iii | 2.189 (3) | C8—H8 | 0.9300 |
| F1—C7 | 1.365 (4) | C9—C10 | 1.453 (5) |
| O1—C1 | 1.261 (5) | C11—C13 | 1.491 (6) |
| O2—C1 | 1.243 (5) | C11—C12 | 1.492 (7) |
| O3—C10 | 1.264 (4) | C11—H11 | 0.9800 |
| N1—C3 | 1.353 (5) | C12—C13 | 1.495 (7) |
| N1—C4 | 1.387 (5) | C12—H12A | 0.9700 |
| N1—C11 | 1.459 (5) | C12—H12B | 0.9700 |
| N2—C6 | 1.396 (4) | C13—H13A | 0.9700 |
| N2—C17 | 1.443 (5) | C13—H13B | 0.9700 |
| N2—C14 | 1.476 (5) | C14—C15 | 1.521 (5) |
| N3—C16 | 1.461 (5) | C14—H14A | 0.9700 |
| N3—C15 | 1.466 (5) | C14—H14B | 0.9700 |
| N3—Ni1iv | 2.189 (3) | C15—H15A | 0.9700 |
| N3—H3N | 0.861 (10) | C15—H15B | 0.9700 |
| C1—C2 | 1.522 (5) | C16—C17 | 1.521 (6) |
| C2—C3 | 1.363 (5) | C16—H16A | 0.9700 |
| C2—C10 | 1.430 (5) | C16—H16B | 0.9700 |
| C3—H3 | 0.9300 | C17—H17A | 0.9700 |
| C4—C5 | 1.404 (5) | C17—H17B | 0.9700 |
| C4—C9 | 1.402 (5) | ||
| O3—Ni1—O3i | 180.00 (9) | C7—C8—H8 | 119.7 |
| O3—Ni1—O1i | 91.34 (10) | C9—C8—H8 | 119.7 |
| O3i—Ni1—O1i | 88.66 (10) | C4—C9—C8 | 117.4 (3) |
| O3—Ni1—O1 | 88.66 (10) | C4—C9—C10 | 122.7 (3) |
| O3i—Ni1—O1 | 91.34 (10) | C8—C9—C10 | 119.8 (3) |
| O1i—Ni1—O1 | 180.000 (1) | O3—C10—C2 | 126.1 (3) |
| O3—Ni1—N3ii | 93.30 (11) | O3—C10—C9 | 118.4 (3) |
| O3i—Ni1—N3ii | 86.70 (11) | C2—C10—C9 | 115.4 (3) |
| O1i—Ni1—N3ii | 91.38 (11) | N1—C11—C13 | 119.9 (4) |
| O1—Ni1—N3ii | 88.62 (11) | N1—C11—C12 | 119.9 (4) |
| O3—Ni1—N3iii | 86.70 (11) | C13—C11—C12 | 60.2 (3) |
| O3i—Ni1—N3iii | 93.30 (11) | N1—C11—H11 | 115.3 |
| O1i—Ni1—N3iii | 88.62 (11) | C13—C11—H11 | 115.3 |
| O1—Ni1—N3iii | 91.38 (11) | C12—C11—H11 | 115.3 |
| N3ii—Ni1—N3iii | 180.000 (1) | C11—C12—C13 | 59.9 (3) |
| C1—O1—Ni1 | 132.5 (2) | C11—C12—H12A | 117.8 |
| C10—O3—Ni1 | 127.7 (2) | C13—C12—H12A | 117.8 |
| C3—N1—C4 | 119.4 (3) | C11—C12—H12B | 117.8 |
| C3—N1—C11 | 121.3 (3) | C13—C12—H12B | 117.8 |
| C4—N1—C11 | 119.1 (3) | H12A—C12—H12B | 114.9 |
| C6—N2—C17 | 116.4 (3) | C11—C13—C12 | 60.0 (3) |
| C6—N2—C14 | 119.4 (3) | C11—C13—H13A | 117.8 |
| C17—N2—C14 | 110.0 (3) | C12—C13—H13A | 117.8 |
| C16—N3—C15 | 108.6 (3) | C11—C13—H13B | 117.8 |
| C16—N3—Ni1iv | 111.6 (2) | C12—C13—H13B | 117.8 |
| C15—N3—Ni1iv | 119.4 (2) | H13A—C13—H13B | 114.9 |
| C16—N3—H3N | 109 (4) | N2—C14—C15 | 110.6 (3) |
| C15—N3—H3N | 111 (4) | N2—C14—H14A | 109.5 |
| Ni1iv—N3—H3N | 96 (4) | C15—C14—H14A | 109.5 |
| O2—C1—O1 | 124.1 (3) | N2—C14—H14B | 109.5 |
| O2—C1—C2 | 116.9 (3) | C15—C14—H14B | 109.5 |
| O1—C1—C2 | 118.9 (3) | H14A—C14—H14B | 108.1 |
| C3—C2—C10 | 118.9 (3) | N3—C15—C14 | 113.8 (3) |
| C3—C2—C1 | 116.1 (3) | N3—C15—H15A | 108.8 |
| C10—C2—C1 | 124.9 (3) | C14—C15—H15A | 108.8 |
| N1—C3—C2 | 125.4 (3) | N3—C15—H15B | 108.8 |
| N1—C3—H3 | 117.3 | C14—C15—H15B | 108.8 |
| C2—C3—H3 | 117.3 | H15A—C15—H15B | 107.7 |
| N1—C4—C5 | 121.3 (3) | N3—C16—C17 | 114.6 (4) |
| N1—C4—C9 | 118.1 (3) | N3—C16—H16A | 108.6 |
| C5—C4—C9 | 120.6 (3) | C17—C16—H16A | 108.6 |
| C6—C5—C4 | 121.9 (3) | N3—C16—H16B | 108.6 |
| C6—C5—H5 | 119.0 | C17—C16—H16B | 108.6 |
| C4—C5—H5 | 119.0 | H16A—C16—H16B | 107.6 |
| C5—C6—N2 | 122.7 (3) | N2—C17—C16 | 110.1 (3) |
| C5—C6—C7 | 115.6 (3) | N2—C17—H17A | 109.6 |
| N2—C6—C7 | 121.4 (3) | C16—C17—H17A | 109.6 |
| C8—C7—F1 | 117.5 (3) | N2—C17—H17B | 109.6 |
| C8—C7—C6 | 123.8 (3) | C16—C17—H17B | 109.6 |
| F1—C7—C6 | 118.6 (3) | H17A—C17—H17B | 108.2 |
| C7—C8—C9 | 120.5 (3) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···O2v | 0.861 (10) | 2.48 (4) | 3.184 (4) | 139 (5) |
| Symmetry codes: (v) −x, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···O2i | 0.861 (10) | 2.48 (4) | 3.184 (4) | 139 (5) |
| Symmetry codes: (i) −x, y+1/2, −z+3/2. |
The authors acknowledge financial support by the Science Foundation of Qiqihar Medical University (grant No. 20044405).
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Ciprofloxacin (1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo -7-(1-piperazinyl)-3-quinoline carboxylic acid, H-cf) is a member of a class of quinolones that is used to treat infections (Mizuki et al., 1996). Manganese(II), zinc(II) and copper(II) derivatives of H-cf have been reported (Xiao et al., 2005; An et al., 2007). The title compound nickel(II) derivative is a two-dimensional coordination polymer in which the anion acts in a bridging mode (Fig. 1).
The Ni(II) atom is coordinated by four oxygen atoms and two N atoms from four cf ligands (two monodentate-N and two O,O-bidentate) to form a square grid propagating approximately in the bc plane (Fig. 2).